CN107739594A

CN107739594A - The composition of the alkene substituted containing difluoromethane and fluorine

Info

Publication number: CN107739594A
Application number: CN201710711667.6A
Authority: CN
Inventors: R.赫尔斯; R.R.辛格; J.贝克; R.G.理查; R.S.巴苏; H.T.范; I.尚克兰
Original assignee: Honeywell International Inc
Current assignee: Honeywell International Inc
Priority date: 2008-07-30
Filing date: 2009-07-30
Publication date: 2018-02-27
Anticipated expiration: 2029-07-30
Also published as: KR20170081148A; CN101665681B; KR20160053854A; KR101754657B1; KR20100013288A; JP2024026168A; JP5770969B2; CA2674256C; JP2015163700A; JP6133921B2; MX2009008204A; CA2674256A1; MX2019009273A; JP2010047754A; JP2021036045A; JP6799039B2; MX340764B; CN104059613A; KR20180018601A; JP2017036452A

Abstract

The present invention discloses the composition containing multi-fluoro olefins and HFC 32.Such composition is used in particular for fixing refrigeration and air-conditioning equipment.

Description

The composition of the alkene substituted containing difluoromethane and fluorine

The application is divisional application, and it is July 30, Application No. in 2009 applying date that its female case, which is, The application of the 201410210405.8th, entitled " composition of the alkene substituted containing difluoromethane and fluorine ".The division Shen Please be also divisional application, it is July 30, Application No. 200910163337.3, denomination of invention in 2009 applying date that its female case, which is, For the application of " composition of the alkene substituted containing difluoromethane and fluorine ".

Related application

The application is related to and required the international application no PCT/ submitted on July 3rd, 2008 (as part continuation application) US2008/069139 priority, the latter require 11/773959 priority submitted on July 6th, 2007 again successively.This Shen It please be directed to (as part continuation application) and require the following priority per a U. S. application：On June 26th, 2006 submits While pending U.S. Application No. 11/475605, it requires the provisional application 60/ submitted on June 24th, 2005 successively 693853 priority, and it is directed to the following application per a United States Non-Provisional (regular) as part continuation application：10/ 694,273；10/695,212；10/694,272, these applications were submitted per a on October 27th, 2003.The application It is related to and requires the following priority per a U. S. application：On March 20th, 2006 submits U.S. Application No. 11/385,259 (in currently examining), it requires that the rights and interests for the U.S. Application No. 10/695,212 submitted on October 23rd, 2003 are (existing successively Abandon)；Examining 11/757782 submitted with June 4th, 2006, it requires that on October 27th, 2003 submits successively The U.S. Application No. 10/694,272 examined priority.The application also relates to and require following and face per a U.S. When the priority applied：The U.S. Provisional Application No. 61/099,382 and on July 30th, 2008 that September in 2008 is submitted on the 23rd carry The U.S. Provisional Application No. 61/084,997 of friendship.Specifically mentioned every part application is as hereinafter thrown a flood of light in this paragraph Equally, it is incorporated herein by reference.

Invention field

The present invention relates to composition, the method and system in numerous applications with effectiveness, including especially heat transfer system Such as refrigerating system.At preferable aspect, the present invention relates to contain difluoromethane and at least one multi-fluoro olefins (multi- Fluorinated olefin) and/or at least one fluorine iodine hydrocarbon (fluoroiodocarbon) refrigerant compositions, and It is related to such preferable purposes of the composition in fixed refrigeration and air-conditioning equipment.

Background

It has been found that fluorine hydrocarbon-based fluids are widely used in many commercial and industrial applications, including as system such as air-conditioning, heat Working fluid in pump and refrigerating system, for example as aerosol propellant, as foaming agent (blowing in these purposes Agents) and as gaseous dielectric medium (gaseous dielectrics).

The promising heat-transfer fluid of in the market must is fulfilled for the property of some very special physics, chemistry and economic aspect Matter, and the very strict combination of the property of physics, chemistry and economic aspect must is fulfilled in some cases.It is moreover, existing There are many different types of heat transfer systems and heat-transfer equipment, and in many cases, it is important that the heat transfer for such system Fluid should have the specific combination for the various properties for meeting peer machine needs.For example, the system based on steam compression cycle It is usually directed to the phase transformation of refrigerant, i.e., under relatively low pressure, refrigerant is changed into by steam phase by liquid by heat absorption, and The compressed steam under relatively elevated pressure, it is by removing heat under such relatively elevated pressure and temperature, the steam is cold Liquid phase is congealed into, then decompression restarts the circulation.

It is preferred such as refrigerant for example, for many years, some fluorohydrocarbons have been many heat-exchange fluids in numerous applications Composition.Fluoric ether, such as chlorofluoromethane and chlorine fluoroethane, due to their unique chemical and physical features (such as thermal capacitance, flammable Property, stability in the operating condition, and with the lubricant (if using any lubricant) for the system can Miscibility) combination, include being widely applied already as refrigerant in air-conditioning and heat pump application in application.Moreover, It is generally used for the either single composition flows of many refrigerant of steam compression system, or it is non-azeotrope, azeotropic mixed Compound.

In recent years, about the concern increase to earth atmosphere and the potential hazard of weather, and in this respect, Mou Xieji It has been accredited as in the compound of chlorine especially problematic.Chloride composition (such as CFC (CFCs), HCFC (HCFCs) Deng) as the refrigerant in air-conditioning and refrigerating system purposes due to the ozone depletion characteristic relevant with many such compounds And become to be out of favour.

Therefore, have increasingly for the alternative new fluorohydrocarbon and HFC compound of refrigeration and heat pump application to providing Increased demand.For example, by using the non-chloride refrigerant compounds that will not be damaged the ozone layer, such as HFC (HFCs), replace For chloride refrigerant with update chloride refrigerant system will become there is an urgent need to.

Relevant much existing refrigerant another it is deeply concerned the problem of be that many such products cause global warming Trend.This feature is normally measured as global warming up trend (global warming potential) (GWP).Compound GWP is the chemical substance relative to known reference molecule, i.e. CO₂The amount of (its GWP=1) to the potential contribution of greenhouse effects Degree.For example, following known refrigerant has following global warming up trend：

Refrigerant	GWP
		R410A	1975
R-507	3850
		R404A	3784
R407C	1653

Although each in above-mentioned refrigerant has been demonstrated that in many aspects effectively these materials increasingly become Less preferably, because being increasingly out of favour using the material that 1000 are greater than about with GWPs.Accordingly, there exist to these and its The demand of the substitute of its existing refrigerant with undesirable GWPs.

Accordingly, there exist the ever-increasing demand to new fluorohydrocarbon and HFC compound and composition, these compounds The attractive substitute of the composition to being used for these and other application field so far is should be with composition.For example, By using will not damage the ozone layer, not cause the level of unwanted global warming, and will meet simultaneously such system to as The refrigerant compositions of all other Strict requirements of the material of heat transfer substance substitute existing refrigerant, to update certain A little systems, including chloride and some refrigerating systems containing HFC have become very urgent.

As for performance characteristic, the application has appreciated that, any potential substitute refrigerant must also have many most wide Those characteristics present in the general fluid used, such as excellent conductivity of heat, chemical stability, low or non-toxic, low or non-flammable Property and lubricant compatibility etc..

As for the efficiency used, it is important that it should be noted that refrigerant thermodynamic property or efficiency (energy Efficiency loss) can be by secondary because being had to fossil fuel caused by the increased demand of electric energy using increase Property environment influence.

Moreover, the universally recognized requirement for substitute refrigerant is effective and need not be to using existing refrigeration at present The conventional steam compress technique of agent, such as refrigerant containing CFC carries out mainly engineered.

Therefore, applicants have appreciated that to composition, and the particularly demand of heat transfer compositions, such composition are effective For substantial amounts of application field, including in concentration by vapor compressor heating liquid and cooling system and method, while avoid above-mentioned one kind or more Kind shortcoming.

Applicant have also appreciated that in numerous applications, lubricant compatibility has special importance.More particularly, it is right In the refrigerant fluid of the lubricant compatible with being used in the compressor set for most of refrigerating systems be very there is an urgent need to 's.Unfortunately, many non-chloride refrigerant fluids, including HFC ' s, CFC ' s and HFC ' s all kinds are used in tradition Lubricant, including be relatively immiscible and/or immiscible in such as mineral oil, alkylbenzene or poly- (alpha-olefin).For Make refrigerant fluid-lubricant combination and worked in compression refrigeration, air-conditioning and/or heat pump with required level of efficiency, profit Lubrication prescription should be substantially soluble in refrigerant fluid in wide operating temperature range.Such solubility reduces the viscosity of lubricant And it is allowed to flow more easily through whole system.In dissolubility as shortage, lubricant is intended in refrigeration, air-conditioning or heat Deposited in the coil pipe of the evaporator of pumping system, and other parts of system, so as to reduce the efficiency of system.

For many applications, inflammability is another important properties.I.e. in many applications, including especially pass In heat application, it is considered as using non-combustible or with relatively low flammable composition or important, or must Want.As used herein, term " non-combustible " refers to, according to the ASTM standard E-681 determination methods promulgated in 2002, (it passed through Reference is incorporated herein in) it is determined as incombustible compound or composition.Unfortunately, it may be desirable to combined for refrigerant It is incombustible that many HFC ' s of thing, which are not,.For example, fluoroalkane difluoroethane (HFC-152a) and fluoroolefin 1,1,1- tri- Fluoropropene (HFO-1243zf) is respectively inflammable, thus can not individually be efficiently used for many application fields.

It has been proposed that the advanced fluoroolefin of the alkene of the fluorine substitution with least five carbon atom is used as refrigerant. Smutny U.S. Patent number 4,788,352 is related to the C of the fluorination with degree of unsaturation at least to a certain degree₅-C₈Compound Preparation.Smutny patent identification is known as having as refrigerant, insecticide, dielectric fluid, heat-transfer fluid, solvent With such higher alkene of the purposes of the intermediate in various chemical reactions.(see the 1st column, 11-22 rows).

Although the fluorinated olefins of Smutny descriptions can have validity to a certain degree in heat transfer applications, it is believed that such Compound can also have some shortcomings.For example, some in these compounds can be intended to attack substrate (substrates), Particularly general-purpose plastics such as acrylic resin and ABS resin.Moreover, the higher olefinic compounds of Smutny descriptions are answered some Can also be less desirable in, because the result of the biocidal activity as Smutny descriptions, may occur in which such The genotoxic potential of compound is horizontal.Moreover, such compound can have too high boiling point, so that they lead in some applications Domain cannot act as refrigerant.

General introduction

According to an aspect of the present invention, it is found by the applicant that above-mentioned one or more need, and possible other need Can be by composition, preferably heat transfer compositions, and even more preferably contains second group of difluoromethane (R-32) and at least one The heat transfer of (and being made up of substantially difluoromethane and at least one second component in certain preferred aspects) is divided to combine Thing and system and be met, the second component is selected from C2-C5 multi-fluoro olefins, preferably comprise at least a kind of C3-C5 tetra--or five- Fluoroolefins, and even more desirably at least a kind of tetrafluoropropene.In the highly preferred embodiment of this aspect of the present invention, extremely A kind of few C3-C5 multi-fluoro olefins, which contain (and containing substantially in certain embodiments) one or more, has end-CF3 Part and the unsaturated ends carbon compound with no more than a fluoro substituents.In highly preferred embodiment, This composition includes (and this method use) difluoromethane (R-32) and 1,1,1,3- tetrafluoropropene (HFO-1234ze, including All isomers) and/or 1,1,1,2- tetrafluoropropenes (HFO-1234yf) and/or 1,2,3,3,3- pentafluoropropenes (HFO 1225ye)。

There is embodiment of the present invention of at least one Br substituents, the preferably change for wherein more fluoric compounds Compound does not include hydrogen.In such embodiments, generally further preferably Br substituents are on unsaturated carbon, and even more preferably Br substituents are on non-end unsaturated carbon.One embodiment of the type is CF₃CBr=CF₂, including all isomeries Body.

In certain embodiments, the composition is also selected from C2-C3 fluoric ethers, CF comprising at least one₃I, and it Combination third component.As used herein, term " fluoro C2-C3 alkane " means there is 2 or 3 carbon atoms and extremely The alkane of few fluoro substituents.In the certain preferred embodiments of this aspect of the invention, second and/or third component As inflammability weakening agent (flammability reducing agent).As used herein, term inflammability weakening agent Refer to the inflammability relative to single difluoromethane, compound or the change with the flammable net effect for reducing said composition The combination of compound.In certain preferred aspects, third component is selected from fluoroethane class.

Term " HFO-1234 " is used to herein refer to all tetrafluoropropenes.The tetrafluoropropene includes 1,1,1,2- tetra- Two kinds of isomers of fluoropropene (HFO-1234yf) and cis and trans 1,1,1,3- tetrafluoropropenes (HFO-1234ze).Term Whether HFO-1234ze is used to be often referred to 1,1,1,3- tetrafluoropropene herein, be cis-or trans-forms but regardless of it.Term " cis HFO-1234ze " and " trans HFO-1234ze " be used for herein with describe respectively 1,1,1,3- tetrafluoropropenes it is cis- And trans-forms.Therefore, term " HFO-1234ze " includes cis HFO-1234ze, trans HFO- in the range of it 1234ze, and all combinations of these isomers and mixture.

The present invention also provides the method and system using the present composition, includes the method and system of heat transfer, Yi Ji The method and system of existing heat-transfer fluid, and selection are substituted in HFO-1225 heat transfer systems according to the heat transfer stream of the present invention The method that body replaces one or more HFO-1225 heat-transfer fluids.In preferred embodiments, the heat transfer for selecting to substitute The method and system of fluid includes selection heat-transfer fluid, to substitute the biography in HFO-1225 heat transfer systems below one or more Hot fluid：R-22, R-134a, R-404A, R-407C, R-410A, R-507, and any two of these fluids or more kind Combination.

Brief description

Fig. 1-12 is the every kind of of ternary composition (it displays that the binary composition of some preferred compositions of the present invention) The curve map that the capacity of capacity of the component in various concentrations and known refrigerant matches substantially, as described in embodiment.

The detailed description of preferred embodiment

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The application includes at least following embodiment：

1. heat transfer compositions, it is included：

(a) the first component of difluoromethane (R-32) is included；

(b) it is selected from the second component of C2-C5 multi-fluoro olefins；

(c) and optionally at least one third component, the third component are selected from C2-C3 fluoric ethers, CF₃I, and it Combination.

2. the heat transfer compositions of embodiment 1, wherein second component includes at least one C3-C5 tetra--or five-fluorine Alkene.

3. the heat transfer compositions of embodiment 1, wherein second component, which includes at least one, has end-CF₃Part With the C3-C5 tetra--or five-fluoroolefins of the unsaturated ends carbon with no more than a fluoro substituents.

4. the heat transfer compositions of embodiment 3, wherein second component, which includes at least one, has end-CF₃Part With the C3-C5 tetra--or five-fluoroolefins of the unsaturated ends carbon with no more than a fluoro substituents, including 1,1,1,3- tetrafluoro Propylene (HFO-1234ze).

5. the heat transfer compositions of embodiment 4, wherein at least one has end-CF₃Part and with being no more than The C3-C5 tetra--or five-fluoroolefins of the unsaturated ends carbon of one fluoro substituents include 1,1,1,3- tetrafluoropropenes (trans HFO- 1234ze)。

6. the heat transfer compositions of embodiment 5, wherein the composition include from the HFC-32 of the weight of about 3- about 98% and From the trans HFO-1234ze of the weight of about 2- about 97%, it is each pressed relative to the trans HFO-1234ze in said composition Determined with HFC-32 gross weight.

7. the heat transfer compositions of embodiment 5, wherein the composition includes the HFC-32 from the weight of about 45- about 55% With the trans HFO-1234ze from the weight of about 45- about 55%, it is each pressed relative to the trans HFO- in said composition 1234ze and HFC-32 gross weight measure.

8. the heat transfer compositions of embodiment 5, wherein the composition includes the HFC-32 from the weight of about 70- about 95% With the trans HFO-1234ze from the weight of about 5- about 30%, it is each pressed relative to the trans HFO- in said composition 1234ze and HFC-32 gross weight measure.

9. the heat transfer compositions of embodiment 5, wherein the composition include from the HFC-32 of the weight of about 3- about 20% and From the trans HFO-1234ze of the weight of about 80- about 97%, it is each pressed relative to the trans HFO-1234ze in said composition Determined with HFC-32 gross weight.

10. the heat transfer compositions of embodiment 3, wherein second component, which includes at least one, has end-CF₃Portion Point and C3-C5 tetra--or five-fluoroolefins with the unsaturated ends carbon for being no more than fluoro substituents, including 1,1,1,2- tetra- Fluoropropene (HFO-1234yf).

11. the heat transfer compositions of embodiment 10, wherein the composition includes the HFC- from the weight of about 10- about 90% The 32 and HFO-1234yf from the weight of about 10- about 90%, its each press relative to the HFO-1234yf in said composition and HFC-32 gross weight measure.

12. the heat transfer compositions of embodiment 11, wherein the composition includes the HFC- from the weight of about 20- about 40% The 32 and HFO-1234yf from the weight of about 60- about 80%, its each press relative to the HFO-1234yf in said composition and HFC-32 gross weight measure.

13. the heat transfer compositions of embodiment 11, wherein the composition includes the HFC- from the weight of about 70- about 90% The 32 and HFO-1234yf from the weight of about 10- about 30%, its each press relative to the HFO-1234yf in said composition and HFC-32 gross weight measure.

14. the heat transfer compositions of embodiment 11, wherein the composition include the less than about HFC-32 of 3% weight and From the HFO-1234yf of the weight of about 95- about 99.5%, it is each pressed relative to the HFO-1234yf and HFC- in said composition 32 gross weight measure.

15. the heat transfer compositions of embodiment 11, wherein the third component be present, and it is selected from fluoroethane, fluoro Alkene, and the combination of any two of these compounds or more kind.

16. the heat transfer compositions of embodiment 1, wherein first component, second component and described 3rd group Point, when third component be present, effectively to provide the presence of the amount of heat transfer compositions, make the capacity of the composition substantially not low In at least one of R-22, R-404A, R-407C, R-410A or R-507, and the group of their any two or more kind Close the capacity in cryogenic applications.

17. the heat transfer compositions of embodiment 1, wherein first component, second component and described 3rd group Point, when there is third component, effectively to provide the presence of the amount of heat transfer compositions, the capacity of the composition is not less than substantially At least one of R-22, R-134a, R-404A, R-407C, R-410A or R-507, and their any two or more kind Combination medium temperature application in capacity.

18. transferring heat to fluid or body or the method spread out of from fluid or body, this method includes making embodiment 1 Composition phase transformation simultaneously carries out heat exchange during the phase transformation with the fluid or body.

19. including the refrigerating system of the composition according to embodiment 1, the system is selected from automotive air conditioning systems, lived Residence air-conditioning system, market air-conditioning system, house refrigerator system, residential refrigerator systems, market refrigerator system, market refrigerator system, Cooler air-conditioning system, cooler refrigerating system, heat pump, and the combination of they two or more.

20. selecting the method for the composition for existing heat transfer system, this method includes：

A) existing heat transfer system is analyzed in a manner of the fluid displacement approached used in existing heat transfer system fully allowed；

B) capacity of two or more heat transfer compositions is approached, described two or more kind compositions include：

(i) the first component of difluoromethane (R-32) is included；

(ii) it is selected from the second component of C2-C5 multi-fluoro olefins；

(iii) and optionally at least one third component, it is selected from C2-C3 fluoric ethers, CF₃I, and combinations thereof； With

C) at least one of described two or more kind heat transfer compositions for existing heat transfer system is selected.

21. heat transfer compositions, it is included：

(a) fluoroolefin of at least one Formulas I：

Wherein each R stands alone as Cl, F, Br, I or H,

R ' is (CR₂)_nY,

Y is CRF₂,

It is 0 or 1 with n, and

(b) difluoromethane (HFC-32).

22. the heat transfer compositions of embodiment 21, it has the global warming up trend (GWP) no more than about 1000.

23. the composition of embodiment 21, wherein at least one fluoroolefin includes at least one tetrafluoropropene (HFO-1234)。

24. the heat-transfer fluid of the composition comprising embodiment 21, wherein the composition includes at least about 70% weight Foundation formula 1 compound and at least about HFC-32 of 5% weight.

Composition

One advantage of certain embodiments of the present invention is to provide with abnormal flammable composition, while in institute Retain other important characteristics in the range of needing.It can be surveyed at room temperature applicants have appreciated that both R-32 and HFO-1234yf have The flammability limit (flame limits) of amount.However, applicant have observed that, the burning risk of compound in the present composition (flame hazard) is seemingly better than other HFCs such as R-152a and HCs such as R-290.One to be sorted to the inflammability of these materials Individual method is to measure the flame speed of every kind of compound.(Jabbour) R-32, R-152a and R-290 maximum flame is reported Speed is respectively 6.7,23.0 and 38.5cm/s.HFO-1234yf flame speed is tested to be 1.5cm/s.Flame speed is surveyed Amount is designed to measure at room temperature.Because HFO-1234yf is non-flammable at room temperature, flame speed can not with it is other Value directly compares, it is anticipated that flame speed of HFO-1234ze (E) flame speed less than HFO-1234yf should be rational. This will imply that R-32 and HFO-1234ze and/or HFO-1234yf mixture will be fast with the flame less than 6.7cm/s Degree.Compared with different materials, if the first material has the lower flame speed of than second material, the first thing Matter is by the possibility with the flame propagation relative to the lower stabilization of second of material.

In preferred embodiments, at least one multi-fluoro olefins compound of the invention is included with compounds of Formula I：

Wherein each R stands alone as Cl, F, Br, I or H,

R ' is (CR₂)_nY,

Y is CRF₂,

0,1,2 or 3, preferably 0 or 1 with n, but generally preferably when Br is present in the compound, then the compound Hydrogen-free.In certain embodiments, Br is not present in the compound.

In highly preferred embodiment, Y is CF₃, n be 0 or 1 (being most preferably 0) and remaining Rs (including in R ' Rs at least one in) is F, and preferably R is not Br or in the presence of Br, and the compound is not hydrogeneous.

In general, applicant believes that compound of formula I identified above is typically effective, and typically in heat transfer group In compound and particularly effectiveness is shown in refrigerant compositions.It has also been found that the composition of the present invention is used as foaming agent group Compound, bulking agent, aerosol, propellant, aromatic, fumet, solvent compositions and foaming agent (inflating agent) Composition.However, applicant is taken aback and it was unexpectedly observed that with some compound for the structure for meeting structure above and its Its such compound compares, and shows the low-level toxicity being highly desirable.It can be easily understood that this find with latent Economic advantages and not only preparing refrigerant compositions, but also preparing containing meeting some phases of structure above To there is benefit during any and all composition of toxic chemical.More particularly, applicant believes that, with respect to low toxicity levels Relevant with Formula II compound, Y is CF preferably wherein₃, n is 0 or 1, wherein at least one R on unsaturated ends carbon is H, At least one in remaining Rs is F or Cl.Applicant is it is also believed that all structures, geometry and the alloisomerism of such compound Body is all effective and advantageously has hypotoxicity.

In certain preferred aspects, multi-fluorinated compounds of the invention include C3 or C4 hydrogen perhaloalkenes (hydrofluorochloroolefin) (" HFCO "), especially C3HFCO, and more preferably according to the compound of Formulas I, wherein Y It is CF₃, n is 0, and at least one R on unsaturated ends carbon is H, and at least one in remaining Rs is Cl.HFCO- 1233 be an example of such preferred compound.

In highly preferred embodiment, particularly in the embodiment containing above-mentioned low toxicity compounds, n is 0.In some highly preferred embodiments, composition of the invention includes one or more tetrafluoropropenes, including HFO- 1234yf, (cis) HFO-1234ze and (trans) HFO-1234ze, and the group of two or more in these compounds Close.(although cis) HFO-1234ze and (trans) HFO-1234ze characteristic is different, the phase at least some of aspect These compounds are hoped to be each suitable for either independent or be used for together with other compounds (including its stereoisomer) above-mentioned In relevant various applications, method and system.For example, (trans) HFO-1234ze can be due to its relatively low boiling point (- 19 DEG C) It is preferred in some systems, and (cis) HFO-1234ze (+9 DEG C of boiling point) is preferably used in other application.Certainly, it is suitable The combination of formula-and trans-isomer is likely to be acceptable and/or preferable in many embodiments.Therefore, it should Understanding term " HFO-1234ze " and 1,3,3,3- tetrafluoropropenes refer to any or two kinds of stereoisomers, and the term Using be intended to indicate it is cis-and each of trans-forms be applied to and/or have for the purpose, except as otherwise noted.

HFO-1234 compounds are known material and are listed in chemical abstracts database.Pass through various saturations and insatiable hunger With C containing halogen₃The steam phase fluorination of compound for catalysis prepares fluoropropenes such as CF₃CH=CH₂U.S. Patent number 2 is described in, 889,379；In 4,798,818 and 4,465,786, each piece of these documents is incorporated herein by reference.Also by drawing It is open by elevated temperatures with the EP 974,571 that is incorporated herein in, with the catalyst based on chromium in steam phase, Or KOH, NaOH, Ca (OH) are used in the liquid phase₂Or Mg (OH)₂Alcoholic solution contact 1,1,1,3,3- pentafluoropropanes (HFC- 245fa), 1,1,1,3- tetrafluoropropene is prepared.In addition, the method general description according to the compound of the present invention is prepared in correlation U.S. Patent application (company file number (the H0003789 of co-pending entitled " method for preparing fluoropropenes " (26267) in)), it is incorporated herein in also by reference.

Other preferable compounds for the present invention include pentafluoropropene (including its all isomers (e.g., HFO- 1225)), four-and five-fluorine butylene (including its all isomers (such as HFO-1354 and HFO-1345)).Certainly, it is of the invention Composition contain any two in broad range of the present invention or in any preferable scope of the present invention or more kindization The combination of compound.

The composition of the present invention is believed, particularly comprising HFO-1234's (including HFO-1234ze and HFO-1234yf) Those compositions have the favourable characteristic as some important reasons.For example, applicant believes that (it is at least partially based on mathematics Model), fluoroolefin of the invention to Atmospheric Chemistry by no essential negative effect, compared with some other fluorination materials, It is the negligible factor to ozone depletion.Therefore, preferred composition of the invention, which has, does not substantially cause ozone to consume The advantages of exhausting.Preferable composition does not cause warming for the whole world substantially compared with many hydrofluoroalkanes used at present yet.

Certainly, the other compounds and/or component of the special nature (such as cost) of regulation composition also are included in this In inventive composition, and all such compounds and component are present in the wide scope of the present invention.

In some preferable forms, composition of the invention, which has, is not greater than about 1000, more preferably not greater than about 500, And it is even more preferably no more than about 150 global warming up trend (GWP).In certain embodiments, composition of the invention GWP is not greater than about 100, and even more preferably no more than about 75.As used herein, " GWP " is with relative to carbon dioxide GWP and 100 year visual fields (time horizon) measure, such as in the " scientific evaluation (The of ozone depletion Scientific Assessment of Ozone Depletion), 2002, the global ozone research of World Meteorological association With monitoring plan (World Meteorological Association ' s Global Ozone Research and Monitoring Project) report (its is incorporated herein by reference) defined in ".

In some preferable forms, composition of the invention is it is also preferred that with being not more than 0.05, more preferably no more than 0.02 and even more preferably about 0 ozone depletion potentiality (ODP).As used herein, " ODP " is such as in the " science of ozone depletion Evaluate (The Scientific Assessment ofOzone Depletion), 2002, World Meteorological association it is global smelly Oxygen is studied and monitoring plan (World Meteorological Association ' s Global Ozone Research And Monitoring Project) report (its is incorporated herein by reference) defined in ".

Contained multi-fluoro olefins, particularly compound of formula I, and even more particularly HFO-1234 in the present composition The amount of compound can change in a wide range, and this depends on specific application, and contains and have more than trace and the change less than 100% The composition of compound is in the wide scope of the present invention.Moreover, the composition of the present invention can be azeotropic, azeotropic mixture sample Or non-azeotrope.In preferred embodiments, this composition includes compound of formula I, preferably HFO-1234 and more preferably HFO-1234ze and/or HFO-1234yf, preferably HFO-1234ze and/or HFO-1234yf amount are from about 5% weight-about 99% weight, and the weight of more preferably from about 5% weight-about 95%.Many other compounds or component, including it is lubricant, steady Determine agent, metal deactivator, corrosion inhibitor, fire retardant (flammability suppressants), and described group of regulation The other compounds and/or component of the special nature (such as cost) of compound may also comprise in the present compositions, and it is all this The compound and component of sample are present in the wide scope of the present invention.

It is expected that the existing amounts of HFC-32 can be extensively varied in the wide scope of the present invention.In preferred embodiment In, based on the heat transfer capacity needed for fluid, will be typically based on will wherein use the amount for the HFC-32 being present in the composition Or the system that fluid be present is selected.Initial design is used or be intended for for wherein composition uses R-22, R- (hereafter (but being never limited to) claims one or more in 134a, R-404A, R-407C, R-410A, R-507 for convenience For embodiment for the system of " existing refrigerant group (refrigerant group) ", difluoromethane is preferably with about 1wt%- about 95wt%, more preferably with the wt% of about 1wt%- about 80, even more preferably with about 3wt%- about 75wt%, and even More preferably it is present in about 5wt%- about 70wt% amount in composition.

In certain preferred aspects, the first component is in addition to comprising R-32, also comprising CO₂, the amount of the latter is preferably not Greater than about 5wt% composition.

Second component of the present composition can also be extensively varied in the wide scope of the present invention.Preferable real Apply in scheme, the second special component and its amount in the composition are based on whole composition and reduce flammable ability Selected.Initial design, which is used or be intended for, for wherein composition uses one kind or more in existing refrigerant group For the embodiment of the system of kind refrigerant, the second component is preferably present in the amount of the composition of the weight of about 5- about 99% In composition.In a further preferred embodiment, the second component exists with the amount of the composition of the weight of about 20- about 95%.

For those embodiments according to second aspect with third component, the amount of third component also may be used To be extensively varied in the wide scope of the present invention.In preferred embodiments, the amount that third component is present in composition Also based on required heat-transfer character, especially and effectively the thermal capacity based on composition is selected, and all such Amount is within the scope of the present invention.In certain preferred aspects, third component of the invention is with the weight of about 1- about 99% The amount of composition be present in heat transfer compositions.As described above, when third component be present, it is preferably fluoroethane, excellent Select a fluoroethane (HFC-161), Difluoroethane (HFC-152a), HFC-143a (HFC-143a), 1,1,1,2- HFC-134as And pentafluoroethane (HFC-125) (HFC-134a).

Therefore, applicants have recognized that, some compositions of the invention can be used in many applications with larger advantage. For example, the present invention includes the method and composition relevant with following application field：Heat transfer applications, foam and foaming agent application, throw Penetrate agent application, Sprayable composition application, sterilizing application, aerosol applications, bulking agent application, aromatic and fumet are applied, Solvent application, clean applications, foaming agent application and other application.Believe that those skilled in the art, will without excessive experiment The present composition can be easily set to be applied to any and whole such application.

Heat transfer compositions

The composition of the present invention applies in general to heat transfer applications, i.e., as heating medium and/or cooling medium, including makees To evaporate cooling agent.

On evaporation cooling application, make the composition of the present invention or directly or indirectly connect with the body to be cooled down Touch, and hereafter be allowed to evaporate while such contact or seethe with excitement, preferable result is in the composition according to the present invention In boiling gas absorbed heat from the body to be cooled down.In such an application, preferably by by liquid spray or being applied to On the body of cooling, the composition of the composition, preferably fluid form of the present invention is used., can in other evaporation cooling applications It is preferred that make to escape into relatively low pressure environment from relative high-pressure bottle according to the fluid composition of the present invention, wherein cold But body or directly or indirectly the container with the fluid composition equipped with the present invention contacts, preferably need not recovery or Recompress escaping gas.A special applications to this type of implementation are beverage, food variety, fresh article etc. From cooling (selfcooling).Before invention described herein, previous composition, such as HFC-152a and HFC- 134a was once used in such apply.However, such composition is negatively treated in such application recently, because will These substance releases can cause negative environment to influence into air.For example, the high global warming properties due to these chemicals And can because of its use and caused by the illeffects of environment, U.S. EPA using such it is determined that first had in this application Chemicals is unacceptable.The composition of the present invention is due to its low global warming up trend and low-ozone as described herein The possibility of exhaustion, there will be the advantages of notable in this respect.Additionally, it is desirable to the present composition it has also been found that with electricity or electronics Element (either during preparation or during accelerated life test) cools down relevant notable effectiveness.In an accelerated aging In experiment, with quick continuous order of order heating and the component is cooled down to simulate the use of the component.Therefore, so Apply semiconductor and computer motherboard (board) production industry in have it is special the advantages of.In this respect, of the present invention group Another advantage of compound is to be expected to be shown as touch (contagious) electricity when they are used for relevant such application Learn characteristic.Another kind evaporation cooling application includes temporarily causing liquid stream to interrupt the method by pipeline.Preferably, such side Method includes making the pipeline, such as the water pipe that water flows therethrough, is contacted with according to the fluid composition of the present invention, and make the present invention's Fluid composition is evaporated while conduit is contacted, and to freeze liquid contained therein, and thus temporarily prevents liquid stream from leading to Piping.Such method has can be to such conduit, or connects the system of these conduits in the position of this composition of administration Downstream position carry out the remarkable advantage of relevant maintaining or other pending work.

While it is desirable to the compound of the invention that the composition of the present invention can include wide scope amount, it is generally preferable to the present invention Refrigerant compositions include at least about 50% weight, and the even more preferably at least about root of the amount of the composition of 70% weight According to the compound of Formulas I, and even more preferably HFO-1234 (including HFO-1234ze and HFO-1234yf).In some embodiment party In case, preferably heat transfer compositions of the invention include trans HFO-1234ze.In certain preferred aspects, preferably originally The heat transfer compositions of invention include at least about 80% weight, and the even more preferably at least about HFO-1234 of 90% weight, and very To more preferably HFO-1234yf and/or HFO-1234ze.In certain embodiments, heat transfer compositions of the invention include suitable Formula HFO-1234ze and trans HFO-1234ze, it is preferably cis:Trans weight ratio is from about 1:99- about 10:99, more preferably from about 1:99- about 5:95, and even more preferably from about 1:99- about 3:97.

The relative quantity for the HF hydrocarbon that the present invention uses, which preferably selects generation, to be had required heat transfer capacity, particularly cools down Capacity, and the preferably both heat-transfer fluid of non-combustible.As used herein, term " non-combustible " refers to as passed through ASTM E-681 measure, in atmosphere with non-combustible fluid existing for all proportions.

The composition of the present invention, which can include, to be used to promote and provide some features to composition, or in some cases Reduce other components of the cost of composition.For example, according to the refrigerant compositions of the present invention, in particular for both vapor compression Those components of system, including it is typically about the lubricant of the amount of the composition of the weight of 30- about 50%.Moreover, the group of the present invention Compound can also include co- refrigerant (co-refrigerant), or bulking agent, such as propane, for increasing the compatible of lubricant Property and/or deliquescent purpose.Such bulking agent, including propane, butane and pentane, preferably with the weight of about 0.5- about 5% The amount of composition is present.The combination of surfactant and solubilizer also is added in this composition, with the dissolving of increase oil Degree, such as U.S. Patent number 6, disclosed in 516,837, disclosure of the documents is incorporated herein by reference.For using The usually used refrigeration lubricant such as polyalcohol of the refrigerator of HFC (hydrofluorocarbon) (HFC) refrigerant Ester (Polyol Esters) (POEs) and poly- alkane glycol (Poly Alkylene Glycols) (PAGs), PAG oil, silicone oil, ore deposit Thing oil, alkylbenzene (ABs) and poly- (alpha-olefin) (PAO) can use refrigerant compositions of the invention.The ore deposit being commercially available Thing oil includes Witco LP 250 (registration mark), the Zerol 300 purchased from Shrieve Chemical purchased from Witco (registration mark), the Sunisco 3GS purchased from Witco and the Calumet R015 purchased from Calumet.The alkyl being commercially available Benzene lubricant includes Zerol 150 (registration mark).The ester being commercially available includes dimethyltrimethylene glycol dipelargonate (dipelargonate), it can be used as Emery 2917 (registration mark) and Hatcol 2370 (registration mark) to obtain.It is other Useful ester includes phosphate, dibasic acid ester and fluoroester.In some cases, alkyl oil is to by idohydrocarbon (iodocarbon) refrigerant of composition has enough solubility, and the combination of idohydrocarbon and hydrocarbon ils may be than other types of Lubricant is more stable.Therefore, such combination can have the advantage that.Preferable lubricant includes poly- alkane glycol and ester.Poly- alkane glycol It is highly preferred in certain embodiments, because they are currently used for special application field such as movable air conditioner (mobile air-conditioning).Certainly, the different mixtures of different types of lubricant can be used.

In certain preferred aspects, heat transfer compositions include the compound of formula I from the weight of about 10%- about 95%, More preferably one or more HFO-1234 compounds, and the R-32 from the weight of about 5%- about 90%.

Therefore, method of the invention, system and composition apply in general to relevant broad category of heat transfer system and spy It is not refrigerating system, such as air-conditioning (including both fixed and movable air conditioner systems), causes cold and heat pump systems.Some excellent In the embodiment of choosing, composition of the invention is used for fixed refrigerating system, and such as fixed air-conditioning device and initial design make With one or more fixed refrigerating systems in R-22, R-134a, R-404A, R-407C, R-410A, R-507.This hair Bright preferred embodiment be intended to show these existing refrigerant it is many needed for features, including with HFO-1225 refrigeration GWP equally low or lower the GWP of agent and high or higher capacity as the capacity of such refrigerant and substantially similar In or match substantially, and capacity preferably high as such refrigerant or higher than such refrigerant.Particularly, applicant has been Recognize, the certain preferred embodiments of the present composition are intended to show relatively low global warming up trend (" GWPs "), preferably less than about 1000, more preferably less than about 500, and even more preferably less than about 150 business refrigerating system Deng.

Current many existing refrigerating systems are applied to relevant existing refrigerant, it is believed that composition of the invention can be through repairing Change and be applied to many such systems (either modify through system or modified without system).

In general, preferable heat transfer compositions of the invention are in most of scope of used temperature and pressure, And may all be non-azeotrope in gamut.In other words, the mixture of each component, which produces, has non-constant boiling temperature Liquid, therefore in evaporator and condenser produce be referred to as " temperature glide (temperature glide) " phenomenon." temperature Degree sliding " is that the temperature occurred in non-azeotrope material condensation or evaporation changes.This sliding is preferred to be considered with the present invention's It is relevant in terms of method and composition, to provide the composition most effectively to match with the refrigerant compositions substituted.Single In component or azeotropic mixture, temperature glide 0.R-407C is a kind of zeotrope, and it has 5 in typical applications DEG C sliding, and in certain preferred aspects, this composition produces under conditions of practical application or expected use About 5 DEG C or lower temperature sliding.

It is also believed that this composition is suitable as many combinations currently used for other application (such as aerosol, foaming agent) The substitute of thing, as illustrated in this paper other places.

The particularly preferred embodiment of the composition of the present invention is as described below.

Composition based on HFC-32/HFO-1234yf

In a preferred embodiment in accordance with this invention, the composition includes the first component for accounting for major portion, and It is preferred that substantially by and being even more preferably made up of HFC-32, and the second component includes and preferably substantially by and even more preferably It is made up of HFO-1234yf.In such embodiments, the gross weight meter based on HFC-32 and HFO-1234yf, it is general excellent The amount for selecting HFC-32 to be present in composition is the composition of the weight of about 10- about 90%, the weight of even more preferably about 20- about 90% Composition, and the composition of the weight of even more preferably about 25- about 85%.However, applicant have observed that, in some implementations In scheme, preferably even less than the HFC-32 of 10% weight.For example, for being wherein intended to using the composition or will combine For those embodiments of substitute of the thing as HFC-134a, it is usually preferred to relatively small amount is included in composition, it is such as small In about 5% and even more preferably less than about 3% HFC-32.In fact, in some such HFC-134a alternate embodiment In, it is probably desirable comprising a certain amount of HFC-32 in composition, the amount, which is less than, is based on HFC-32 and HFO-1234yf Gross weight meter 1%.

As described above, the composition in such preferred embodiment also includes the second component containing HFO-1234yf. In some such embodiments, the second component includes the HFO-1234yf of major portion, and preferably substantially by and even more It is preferred that it is made up of HFO-1234yf.The amount for the HFO-1234yf being present in composition is preferably from the weight of about 10- about 90% The composition of the weight of composition, more preferably from about 10- about 80%, and even more preferably from the combination of the weight of about 15- about 75% Thing.

According to some preferred embodiments of the present invention, particularly or relate preferably to wherein composition and be intended to serve as R-404A substitute (replacement) or the embodiment of substitute (alternative), are present in composition HFO-1234yf amount, it is from the weight of about 40%- about 80%, more preferably based on HFO-1234yf and HFC-32 gross weight meter From the weight of about 50%- about 80%, and the weight of even more preferably about 60%- about 80%.It has been found by the applicant that within the range Composition provide there is the global warming up trend more much lower than many standard refrigerants (including R-410A and R-404A) (GWP) showing, and simultaneously commercially can be with such previously used refrigerant (including being particularly R-410A and R-404A) The refrigerant fluid of the performance parameter to compare.One of such performance is measured by 95 °F of environment temperatures and AHRI " A " condition There is provided.According to such measurement, applicant surprisingly and/or is advantageously discovered that, containing from the weight of about 30- about 50% HFO-1234yf (relative to HFO-1234yf in the composition and HFC-32 gross weight) present composition can provide with For the matched well of the parameter of refrigerant such as R-22 discharge temperature, at the same still reach it is relevant with capacity and efficiency can The performance parameter of receiving.For such embodiment, the HFO-1234yf of the weight containing about 35- about 45%, and it is even more excellent Select the composition of the HFO-1234yf containing about 40% weight (relative to HFO-1234yf in composition and HFC-32 gross weight) It is particularly preferred.

According to some preferred embodiments of the present invention, the amount for the HFO-1234yf being present in composition, based on group The gross weight meter of HFO-1234yf and HFC-32 in compound, it is that and more preferably from about 20- is about from the weight of about 10%- about 50% 40% weight, and the weight of even more preferably about 10%- about 30%.It has been found that the composition in the range of these carries For with the global warming up trend (GWP) more much lower than many standard refrigerants (including R-404a and R-410A), and show simultaneously Showing commercially can be compared with such previously used refrigerant (including being particularly R-410A, R-404a and R-22) The refrigerant fluid of performance parameter.One of such performance standard measures to be carried by 95 °F of environment temperatures and AHRI " A " condition For.

Applicant surprisingly and/or is advantageously discovered that, containing the HFO-1234yf (phases from the weight of about 60%- about 80% For HFO-1234yf in composition and HFC-32 gross weight) the present composition can provide relative to refrigerant such as The matched well of R-404a capacity and the parameter of efficiency, while still reach the acceptable performance relevant with discharge temperature Parameter.For such embodiment, the HFO-1234yf of the weight containing about 65- about 85%, and even more preferably contain about 70% The HFO-1234yf of weight composition is particularly preferred (relative to HFO-1234yf in composition and HFC-32 gross weight) , especially as R404a substitute.

Applicant surprisingly and/or is advantageously discovered that, (relative containing the HFO-1234yf from the weight of about 10- about 50% The HFO-1234yf and HFC-32 gross weight in composition) the present composition can provide relative to refrigerant such as R- The matched well of 410A capacity and the parameter of efficiency, while still reach the acceptable performance parameter relevant with discharge.It is right In such embodiment, the HFO-1234yf of the weight containing about 20- about 40%, and even more preferably containing about 30% weight HFO-1234yf composition is particularly preferred (relative to HFO-1234yf in composition and HFC-32 gross weight).

Composition based on HFC-32/HFO-1234ze

In a preferred embodiment in accordance with this invention, the composition includes the first component for accounting for major portion, and It is preferred that substantially by and being even more preferably made up of HFC-32, and the second component includes and preferably substantially by and even more preferably By HFO-1234ze, and even more preferably it is made up of trans HFO-1234ze.In such embodiments, it is generally preferred to The amount that HFC-32 is present in composition is the composition of the weight of about 3- about 98%, the weight of even more preferably about 10- about 95% Composition, and even more preferably in certain embodiments, especially it is intended to substitute as or as 404a or 410A It is the composition of the weight of about 40- about 95% in those embodiments.

As described above, the composition in such preferred embodiment also includes the second component containing HFO-1234ze. In some such embodiments, the second component includes the HFO-1234ze of major portion, preferably trans HFO-1234ze, and It is preferred that substantially by and being even more preferably made up of HFO-1234ze (preferably trans HFO-1234ze).It is present in composition HFO-1234ze (preferably trans HFO-1234ze) amount be preferably from the composition of the weight of about 2- about 97%, more preferably from The composition of the weight of about 5- about 90%, and be the combination from the weight of about 5- about 60% even more preferably in certain embodiments Thing.

According to some preferred embodiments of the present invention, the HFO-1234ze being present in composition is (preferably trans HFO-1234ze amount), it is from the weights of about 25%- about 85% based on HFO-1234ze in composition and HFC-32 gross weight meter Amount.It has been found by the applicant that composition within the range is provided with more much lower than many standard refrigerants (including R-410A) Global warming up trend (GWP), and show simultaneously commercially can be with such previously used refrigerant (including particularly R404A, R410A and R-22) refrigerant fluid of performance parameter that compares.One of such performance is measured by 95 °F of rings Border temperature and AHRI " A " condition provide.

According to such measurement, applicant surprisingly and/or is advantageously discovered that, containing from the weight of about 50- about 70% HFO-1234ze (relative to HFO-1234ze in the composition and HFC-32 gross weight) present composition can provide use In the matched well of the parameter of refrigerant such as R-22 discharge temperature, while still reach relevant with capacity and efficiency and connect The performance parameter received.For such embodiment, the HFO-1234ze of the weight containing about 35- about 45%, and even more preferably The composition of HFO-1234ze containing about 55% weight is (relative to HFO-1234ze in composition and HFC-32 gross weight) It is particularly preferred.

According to some preferred embodiments of the present invention, the amount for the HFO-1234ze being present in composition, based on group The gross weight meter of HFO-1234ze and HFC-32 in compound, it is that more preferably from about 5%- is about from the weight of about 5%- about 30% 20% weight, and be even more preferably 10% weight in certain embodiments.It has been found that the group in the range of these Compound and amount, which provide, has the global warming up trend (GWP) more much lower than many standard refrigerants (including R-410A), and simultaneously Showing can commercially join with the performance compared with such previously used refrigerant (including being particularly R-410A and R-22) Several refrigerant fluids.

According to another preferred embodiment, applicant surprisingly and/or is advantageously discovered that, containing from about 5- about The HFO-1234ze (relative to HFO-1234ze in composition and HFC-32 gross weight) of the 30% weight present composition Matched well relative to refrigerant such as R-410A capacity and the parameter of efficiency can be provided, while still reached and discharge temperature Spend relevant acceptable performance parameter.For such embodiment, the HFO-1234ze of the weight containing about 5- about 25%, and The composition of HFO-1234ze even more preferably containing about 10% weight is (relative to HFO-1234ze in composition and HFC-32 Gross weight) be particularly preferred.

According to the present invention some preferred embodiments, especially or preferably include wherein composition be used for plus Enter or be intended to serve as R404A substitute or those embodiments of substitute, the HFO-1234ze's being present in composition Amount, based on HFO-1234ze in composition and HFC-32 gross weight meter, it is from the weight of about 40%- about 70%, is more preferably from about The weight of 40- about 60%, the weight of more preferably from about 45- about 55%, and be even more preferably about 50% in certain embodiments Weight.Have it has been found by the applicant that composition in the scope and content provides than many standard refrigerants (including R- 404A) much lower global warming up trend (GWP), and show simultaneously commercially can be with such previously used refrigerant The refrigerant fluid for the performance parameter that (including being particularly R404A) compares.One of such performance standard is measured by 95 ° F environment temperatures and AHRI " A " condition provide.According to such measurement, applicant surprisingly and/or is advantageously discovered that, contains From the HFO-1234ze (relative to HFO-1234ze in composition and HFC-32 gross weight) of the weight of about 40- about 70% sheet Inventive composition can provide the matched well relative to refrigerant such as R-404A capacity and the parameter of efficiency, while still Reach the acceptable performance parameter relevant with discharge temperature.For such embodiment, the weight containing about 40- about 60% HFO-1234ze, and the composition of the HFO-1234ze even more preferably containing about 50% weight is (relative to HFO- in composition 1234ze and HFC-32 gross weight) it is particularly preferred.

According to the present invention some preferred embodiments, especially or preferably include wherein composition be used for plus Enter or be intended to serve as the embodiment for substituting R-134a substitute, the amount for the HFO-1234ze being present in composition, be based on HFO-1234ze and HFC-32 gross weight meter, it is the weight of more preferably from about 80- about 90% from the weight of about 80%- about 97%, And even more preferably about 85% weight.Have it has been found by the applicant that the composition in the scope and content provides than being permitted The much lower global warming up trend (GWP) of multi-standard refrigerant (including R-134a), and show simultaneously commercially can be with this The refrigerant fluid for the performance parameter that the previously used refrigerant of class (including being particularly R-134a) compares.

Composition based on HFC-32/CF3I

In a preferred embodiment in accordance with this invention, the composition includes the first component for accounting for major portion, and It is preferred that substantially by and being even more preferably made up of HFC-32.In such embodiments, it is generally preferred to HFC-32 is present in Amount in composition is the composition of the weight of about 1- about 60%.

Composition in such preferred embodiment also contains CF₃I the second component.In some such implementations In scheme, the second component includes the CF of large scale₃I, and preferably substantially by and even more preferably by CF₃I is formed.It is present in group CF in compound₃I amount is preferably the composition from the weight of about 5- about 98%.CF is included for wherein the second component₃I and HFO- 1225 both those embodiments, CF₃I and HFO-1225 relative quantity can change in a wide range, but preferably so Embodiment in, CF₃I amount is the composition of the weight of about 5- about 98%, and HFO-1225 amount is the weight of about 1- about 65% Composition.CF is included for wherein the second component₃I and HFO1225 embodiment, third component are optional, but if In the presence of, then preferably with from the amount of the composition of about 1-94% weight exist.The second component is substantially by CF wherein₃I compositions In embodiment, i.e., said composition does not include the HFO-1225 of significant quantity.Then third component is needed and preferably with least about The amount of the composition of 1% weight is present in said composition.

It is expected that the combination of the compound of greater number can be in the particular embodiment, with the various relatively dense of wide scope Third component of the degree as the present invention, and believe that all amounts and combination are applied to tell about according to what is included herein.However, In certain preferred aspects, wherein third component include a fluoroethane (HFC-161), Difluoroethane (HFC-152a), HFC-143a (HFC-143a), 1,1,1,2- HFC-134as (HFC-134a), pentafluoroethane (HFC-125), 1,1,1,3- tetra- Fluoropropene (HFO-1234ze, including all isomers) and 1, one kind in 1,1,2- tetrafluoropropene (HFO-1234yf) or It is a variety of.Such component if it does, it is preferred that its be selected from table 1 below indicated scope (it should be appreciated that the amount indicated before have Modifier " about " and the amount is based on the percentage by weight in composition)：

Table 1

Composition based on HFC-32/HFO-1225

In these embodiments of the present invention, the composition includes the first component for accounting for major portion, and preferred base This HFC-32 by and being even more preferably made up of.In such embodiments, it is generally preferred to HFC-32 is present in composition In amount be the weight of about 1- about 60% composition.

Composition in such preferred embodiment also contains HFO-1225, preferably the second of HFO-1225ye-Z Component.In some such embodiments, the second component includes the HFO-1225 of large scale, and preferably substantially by and even More preferably it is made up of HFO-1225ye-Z.The amount for the HFO-1225ye-Z being present in composition is preferably from about 5- about 98% The composition of weight.In such embodiments, third component is optional, but if in the presence of then preferably with from about 1- The amount of the composition of 94% weight is present.

It is expected that the combination of the compound of greater number can be in the particular embodiment, with the various relatively dense of wide scope Third component of the degree as the present invention, and believe that all amounts and combination are applied to tell about according to what is included herein.However, In certain preferred aspects, wherein third component include a fluoroethane (HFC-161), Difluoroethane (HFC-152a), HFC-143a (HFC-143a), 1,1,1,2- HFC-134as (HFC-134a), pentafluoroethane (HFC-125), 1,1,1,3- tetra- Fluoropropene (HFO-1234ze, including all isomers) and 1, one kind in 1,1,2- tetrafluoropropene (HFO-1234yf) or It is a variety of.Such component if it does, it is preferred that its be selected from table 2 below indicated scope (it should be appreciated that the amount indicated before have Modifier " about " and the amount is based on the percentage by weight in composition)：

Table 2

System of selection

One aspect of the present invention is related to method of the selection for the heat transfer compositions of related existing heat transfer system.Such as As used herein, term " existing heat transfer system " not only includes actual heat transfer system that is constructed and suitably installing positioning, and And the system including not yet building but having conceived and/or in the design phase.One preferred embodiment provides selection and is used for The method of the heat transfer compositions of related existing heat transfer system, the existing heat transfer system be designed to it is previously known The relevant application of composition.In this case, previously known composition will generally have in need or desired thermal capacitance Amount.But also show that one or more do not need characteristic.For example, each of following previously known refrigerant is using it System in there is required thermal capacity, but display that the unwanted high GWP indicated as follows：

Preferable method and step is included sufficiently to allow to approach the heat transfer that (approximation) is existing or designs The parameter of the mode analysis system of fluid displacement, and permission is provided under conditions of existing or design system, approach this hair The instrument of the capacity of two or more bright compositions, and selected using the instrument for existing or design system Composition.The example of such instrument is the chart shown in following examples.Configured according to content is told about contained by this paper Computer program for another kind as instrument example.In preferred embodiments, the instrument can also be approached, surveyed GWP and/or inflammability fixed or that combine the present composition, and select step to include selecting to have being less than about 1000, and even More preferably less than about 150, and/or the composition without inflammability or inflammability in the range of predefined parameter.

Method and system

The composition of the present invention is used in relevant a large amount of method and systems, including as the method for heat transfer and is System, as being used for the heat-transfer fluid in refrigeration, air-conditioning and heat pump.This composition is to system and the side for producing aerosol In method and advantageous, in such system and method, the aerosol preferably comprises aerosol propellant or molten by gas Glue propellant forms.Certain aspects of the invention also include the method for forming foam and fire extinguishing and the method for checking the intensity of a fire. The present invention also provides the method that residue is removed from article in some aspects, and in the article, this composition is such It is used as solvent compositions in method and system.

Heat-transferring method and system

Preferable heat-transferring method generally comprises：There is provided the present invention composition and by sensitivity heat transfer, phase-change heat transfer, Or these combination makes the heat to be transmitted be passed to composition or goes out composition outflow.For example, in some preferred of the inventive method Embodiment in, there is provided containing the present invention refrigerant refrigerating system and by condense and/or evaporate the present composition produce The method of raw heat supply or cooling.In certain preferred aspects, methods for cooling, including other fluids are direct Or indirectly cool down, or the method for the direct or indirect cooling of body includes refrigerant combination of the condensation containing the present composition Thing, and hereafter evaporate the refrigerant compositions near article to be cooled.As used herein, term " body " is anticipated It is intended to refer not only to do not have lived object, and refers to living tissue, generally comprises animal tissue and particularly tissue.Example Such as, for one or more therapeutic purposes, certain aspects of the invention are related to application of this composition to tissue, such as make For analgesic techniques, as prepared anesthetic, or as be related to reduce treat patient body temperature therapy a part. In some embodiments, the application to body includes under stress, preferably in the pressurization comprising one-way release valve and/or nozzle holding In device, there is provided the present composition of liquid form, and by spray or other means from pressurizing vessel discharge the liquid and It is applied to body.When liquid is from the surface evaporation being atomized, surface cooling.

Some preferable methods for heating liquid or body are included in the liquid to be heated or body is condensed around contains this hair The refrigerant compositions of bright composition, and hereafter evaporate the refrigerant compositions.According to disclosure herein, this area skill Art personnel easily will can be heated and be cooled down according to article of the invention, and need not excessive experiment.

It has been discovered by the applicants that in the system and method for the present invention, many important refrigerating system performance parameters are relative Close to the parameter of above-mentioned existing refrigerant group.It will be appreciated by those skilled in the art that low GWP and/or low-ozone exhaust refrigeration The remarkable advantage of agent, they can be used as to only having the substitute of the refrigerant used in the system seldom modified relatively.It is expected at certain In a little embodiments, the present invention, which provides, to be included replacing existing system with the composition of the present invention (without the system is significantly modified) In heat-transfer fluid (such as refrigerant) update method.In certain preferred aspects, replacement step is simple direct Replace (drop-in replacement), it means substantive redesign that need not be to system and need not more exchange device Major part is to provide the composition of the invention as heat-transfer fluid.In certain preferred aspects, methods described Directly replaced including simple, wherein the capacity of the system is at least about 70% of capacity before replacement, preferably at least about 85%, and Even more preferably at least about 90%, and it is preferably no greater than about 130%, even more preferably less than about 115%, and even more preferably Less than about 110%.In certain preferred aspects, methods described includes simple directly replacement, the wherein suction of the system Pressure and/or discharge pressure (and even more preferably both) for system suction pressures before replacing and/or discharge pressure at least About 70%, more preferably at least about 90%, and even more preferably at least about 95%, and about 130% is preferably no greater than, it is even more excellent Choosing less than about 115%, and even more preferably less than about 110%.In certain preferred aspects, methods described includes letter Easily directly replace, wherein the mass flow of the system is at least about 80% of mass of system flow before replacement, and even more excellent Choosing at least about 90%, and about 130%, even more preferably less than about 115% is preferably no greater than, and even more preferably less than about 110%.

It is preferably to be cooled by evaporating by being absorbed heat from liquid or body in some embodiments of the inventive method Refrigerant compositions of the invention near body or fluid, the steam comprising the present composition is produced to provide cooling.It is preferred that Methods described also includes the other step of compression refrigeration agent steam, generally with compressor reducer or similar devices at relatively high pressure Produce the steam of the present composition.In general, the step of compressed steam causes heat to add in steam, thus causes phase The temperature of high steam is raised.In such composition, the inventive method is included from the relatively-high temperature, high steam Remove at least a portion heat by evaporating and compression step is added.Heat extraction step preferably includes to condense high temperature, high pressure steaming Vapour, and the steam is in relatively high pressure state, to produce the relatively high pressure liquid containing the present composition.Then preferably make This relatively high pressure liquid, which undergoes nominal constant enthalpy in the case where producing the pressure of relative low temperature, low pressure liquid, to be reduced.So Embodiment in, the refrigerant liquid of exactly this cooling after body to be cooled or liquid heat transfer by being evaporated.

In another method embodiment of the present invention, the present composition can be used in the method for heat production, the party Method includes condensing the composition containing refrigerant near hot fluid or body to be added.Such as described previously, such method is often The inverse circulation of above-mentioned refrigerant cycles.

Embodiment

There is provided following examples, it is therefore intended that illustrate the present invention, but do not limit its scope.

Embodiment 1- uses HFC-32 and CF₃I medium temperature system

It is given that the capacity of heat transfer compositions (and particularly refrigerant), which represents cooling or heat capacity and provides compressor, Certain of the refrigerant heat extraction ability of volumetric flow rate is measured.In other words, to given particular compressor, have higher The refrigerant of capacity will transmit stronger cooling or heat capacity.

Simulation refrigeration/air conditioner circulating system simultaneously makes its condenser temperature being furnished be about 40 DEG C, about 2 DEG C of evaporator temperature (about 10 DEG C of overheat, and about 5 DEG C of supercooling), and compressor efficiency are 0.7, and this is considered as normally typical " medium temperature (medium temperature) " conditions.Simulate several compositions of the present invention and/or based on first be made up of HFC-32 Component, by CF₃One of second component of I compositions and a series of third components as described above are tested.For every kind of For three components, it is determined that the relative concentration of all three components matched substantially with R-410A capacity under these conditions.So After draw or simulate (range estimation, mathematical computations, or its combination) capacity for matching substantially with R0410A and correspond to every kind of component The curve of various concentrations.Asterisk on curve represents those compositions with 1000 or less GWP, and positioned at song Rhombus on line represents those compositions with the GWP more than 1000.To all third component compounds specified above and This method is repeated to the second component composition HFO-1225ye-Z.Therefore, " instrument " for the refrigerant that selects the system One example is developed and as shown in the figure in Fig. 1.The chart of analysis chart 1 with identify on curve or curve week Enclose and its GWP be less than about 1000 composition.This identification is preferably carried out before or after the inflammability of analysed composition, Then composition is selected for use as the original components of such system or the substitute as such existing system or Update agent (retrofit).

Embodiment 2- uses HFC-32/CO₂And CF₃I medium temperature system

Embodiment 1 is repeated, the difference is that CO of the first component of heat transfer compositions by 3% weight₂With 97% weight HFC-32 is formed and is R-410A with the refrigerant of its capacity matching.Draw and the chart of analysis chart 2 is to identify in curve Around upper or curve and its GWP is less than about 1000 composition.It is this identification preferably before the inflammability of analysed composition or Carry out, then composition is selected for use as the original components of such system or as such existing system afterwards Substitute or renewal agent.

Embodiment 3- uses HFC-32/CO₂And CF₃I medium temperature system

Embodiment 1 is repeated, the difference is that CO of the first component of heat transfer compositions by 1% weight₂With 99% weight HFC-32 is formed and is R-410A with the refrigerant of its capacity matching.Draw and the chart of analysis chart 3 is to identify in curve Around upper or curve and its GWP is less than about 1000 composition.It is this identification preferably before the inflammability of analysed composition or Carry out, then composition is selected for use as the original components of such system or as such existing system afterwards Substitute or renewal agent.

Embodiment 4- uses HFC-32/CO₂And CF₃I cryogenic system

Embodiment 1 is repeated, the difference is that CO of the first component of heat transfer compositions by 3% weight₂With 99% weight HFC-32 is formed and is R-410A with the refrigerant of its capacity matching, and condition is that condenser temperature is about 45 DEG C, steam temperature Du Yue -34 DEG C (about 10 DEG C of overheats, and about 5 DEG C of supercooling), and compressor efficiency are 0.7, and this is considered as normally allusion quotation " cryogenic conditions " of type.Draw and the chart of analysis chart 4 is to identify on curve or around curve and its GWP is less than about 1000 composition.This identification is preferably carried out before or after the inflammability of analysed composition, and then composition is carried out Selection is for use as the original components of such system or the substitute as such existing system or renewal agent.

Embodiment 5- uses HFC-32/CO₂And CF₃I cryogenic system

Embodiment 1 is repeated, the difference is that CO of the first component of heat transfer compositions by 1% weight₂With 99% weight HFC-32 is formed and is R-410A with the refrigerant of its capacity matching, and condition is that condenser temperature is about 45 DEG C, steam temperature Du Yue -34 DEG C (about 10 DEG C of overheats, and about 5 DEG C of supercooling), and compressor efficiency are 0.7, and this is considered as normally allusion quotation " cryogenic conditions " of type.Draw and the chart of analysis chart 5 is to identify on curve or around curve and its GWP is less than about 1000 composition.This identification is preferably carried out before or after the inflammability of analysed composition, and then composition is carried out Selection is for use as the original components of such system or the substitute as such existing system or renewal agent.

Embodiment 6- uses HFC-32 and HFO-1225 medium temperature system

Simulation refrigeration/air conditioner circulating system simultaneously makes its condenser temperature being furnished be about 40 DEG C, and about 2 DEG C of vapor (steam) temperature is (about 10 DEG C of overheat, and about 5 DEG C of supercooling), and compressor efficiency is 0.7, this is considered as normally typical " medium temperature " bar Part.Simulate several compositions of the present invention and/or formed based on the first component being made up of HFC-32, by HFO-1225ye-Z The second component and a series of one of third components as described above tested.For every kind of third component, it is determined that The relative concentration of all three components matched substantially with R-410A capacity under these conditions.Then draw or simulate (mesh Survey, mathematical computations, or its combination) capacity that matches substantially with R0410A correspond to every kind of component various concentrations curve. Asterisk on curve represents those compositions with 1000 or less GWP, and the rhombus on curve represents Those compositions with the GWP more than 1000.To all third component compounds specified above and to the second component chemical combination Thing CF₃I repeats this method.Therefore, an example for " instrument " of the refrigerant for selecting the system is developed and such as Shown in Fig. 6 figure.The chart of analysis chart 6 is to identify on curve or around curve and its GWP is less than about 1000 Composition.This identification is preferably carried out before or after the inflammability of analysed composition, then composition is selected with Original components as such system or the substitute as such existing system or renewal agent.

Embodiment 7- uses HFC-32 and HFO-1225 cryogenic system

Embodiment 6 is repeated, but condition is that condenser temperature is about 45 DEG C, about -34 DEG C of vapor (steam) temperature (about 10 DEG C of overheat, And about 5 DEG C of supercooling), and compressor efficiency is 0.7, this is considered as normally typical " low temperature " condition.Draw and divide Analyse Fig. 7 chart with identify on curve or around curve and its GWP be less than about 1000 composition.This identification is preferred Carry out, then composition is selected for use as the original of such system before or after the inflammability of analysed composition Beginning component or the substitute as such existing system or renewal agent.

Embodiment 8- uses HFC-32/CO₂With HFO-1225 medium temperature system

Embodiment 6 is repeated, the difference is that CO of the first component of heat transfer compositions by 3% weight₂With 97% weight HFC-32 is formed.Draw and the chart of analysis chart 8 is to identify on curve or around curve and its GWP is less than about 1000 Composition.This identification is preferably carried out before or after the inflammability of analysed composition, then composition is selected with Original components as such system or the substitute as such existing system or renewal agent.

Embodiment 9- uses HFC-32/CO₂With HFO-1225 medium temperature system

Embodiment 6 is repeated, the difference is that CO of the first component of heat transfer compositions by 1% weight₂With 97% weight HFC-32 is formed.Draw and the chart of analysis chart 9 is to identify on curve or around curve and its GWP is less than about 1000 Composition.This identification is preferably carried out before or after the inflammability of analysed composition, then composition is selected with Original components as such system or the substitute as such existing system or renewal agent.

Embodiment 10- uses HFC-32/CO₂With HFO-1225 cryogenic system

Embodiment 6 is repeated, the difference is that CO of the first component of heat transfer compositions by 3% weight₂With 97% weight HFC-32 is formed, and condition is that condenser temperature is about 45 DEG C, about -34 DEG C of vapor (steam) temperature (about 10 DEG C of overheat, and about 5 DEG C Supercooling), and compressor efficiency is 0.7, this is considered as normally typical " cryogenic conditions ".Draw and analysis chart 10 Chart with identify on curve or around curve and its GWP be less than about 1000 composition.This identification is preferably being analyzed Carry out, then composition is selected for use as the original components of such system before or after the inflammability of composition Or the substitute as such existing system or renewal agent.

Embodiment 11- uses HFC-32/CO₂With HFO-1225 cryogenic system

Embodiment 6 is repeated, the difference is that CO of the first component of heat transfer compositions by 1% weight₂With 99% weight HFC-32 is formed, and condition is that condenser temperature is about 45 DEG C, about -34 DEG C of vapor (steam) temperature (about 10 DEG C of overheat, and about 5 DEG C Supercooling), and compressor efficiency is 0.7, this is considered as normally typical " cryogenic conditions ".Draw and analysis chart 11 Chart with identify on curve or around curve and its GWP be less than about 1000 composition.This identification is preferably being analyzed Carry out, then composition is selected for use as the original components of such system before or after the inflammability of composition Or the substitute as such existing system or renewal agent.

Embodiment 12- uses HFC-32 and CF₃I cryogenic system

Embodiment 1 is repeated, but condition is that condenser temperature is about 45 DEG C, about -34 DEG C of vapor (steam) temperature (about 10 DEG C of overheat, And about 5 DEG C of supercooling), and compressor efficiency is 0.7, this is considered as normally typical " cryogenic conditions ".Draw and divide Analyse Figure 12 chart with identify on curve or around curve and its GWP be less than about 1000 composition.This identification is preferred Carry out, then composition is selected for use as the original of such system before or after the inflammability of analysed composition Beginning component or the substitute as such existing system or renewal agent.

Embodiment 13

The vapor liquid equilibrium (VLE) of HFO-1234ze (E) and R-32 mixture is determined by 2 independent methods.First Individual method is the open boiling for the bubble point temperature (bubble point temperature) that mixture is determined under atmospheric pressure Point determination method (it is shown in Table 3).Second method is to allow the sealing system of atmospheric pressure pressure above (it is shown in Table 4).

Table 3：HFO-1234ze (E)+R-32 ebulliometry data

Table 4：HFO-1234ze (E)+R-32 VLE data

Embodiment 14

The VLE of HFO-1234yf and R-32 mixture is determined by 2 independent methods.First method is in big The open hypsometry of the bubble point temperature of mixture is determined under air pressure (it is shown in Table 5).Second method is to allow The sealing system of atmospheric pressure pressure above (it is shown in Table 6).

Table 5：HFO-1234yf+R-32 ebulliometry data

Table 6：HFO-1234yf+R-32 VLE data

Embodiment 15

Using the data of table 3 and 4, performance of these refrigerant in typical air conditioning applications is evaluated.The condition of Air-conditioning Cycle For：

Evaporator temperature=2 DEG C

Condenser temperature=40 DEG C

=5 DEG C of supercooling

=10 DEG C of overheat

Isentropic Compression engine efficiency=0.7

Using these conditions, capacity, COP, compressor exhaust temperature, condenser and evaporator sliding (glides) are calculated And it is shown in table 7A and 7B.Also evaluate the cycle performance of the mixture and GWP and be shown in table 8A and 8B.Use pure R-32's One shortcoming is high exhaust temperature.In all compositions, the sliding of HFO-1234ze (E)+R-32 mixtures is<9 DEG C, And the sliding of the HFO-1234yf+R-32 mixtures in all compositions is<7℃.

Table 7A：The Air-conditioning Cycle analysis of HFO-1234ze (E)+R-32 mixtures

Table 7B：The Air-conditioning Cycle analysis of HFO-1234yf+R-32 mixtures

Table 8A：The heat pump performance of HFO-1234ze (E)+R-32 mixtures

Table 8B：The heat pump performance of HFO-1234yf+R-32 mixtures

Embodiment 16

Using the data of table 3 and 4, performance of these refrigerant in cryogenic applications is evaluated.The condition of low-temperature circulating is：

Evaporator temperature=- 34 DEG C

Condenser temperature=45 DEG C

=10 DEG C of supercooling

=10 DEG C of overheat

Isentropic Compression engine efficiency=0.7

Using these conditions, capacity, COP, compressor exhaust temperature (discharge temperature), condensation are calculated Device and evaporator sliding (glides) are simultaneously shown in table 9A and 9B.Also evaluate the cycle performance of the mixture and GWP and be shown in table In 10A and 10B.A use of pure R-32 shortcoming is high exhaust temperature.In all compositions, HFO-1234ze (E)+ The sliding of R-32 mixtures is<9 DEG C, and the sliding of the HFO-1234yf+ R-32 mixtures in all compositions is<7℃.

Table 9A：The low-temperature circulating analysis of HFO-1234ze (E)+R-32 mixtures

Table 9B：The low-temperature circulating analysis of HFO-1234yf+R-32 mixtures

Table 10A：The cryogenic property of HFO-1234ze (E)+R-32 mixtures

Table 10B：The cryogenic property of HFO-1234yf+R-32 mixtures

Those skilled in the art will be understood that preceding description and embodiment are intended to illustrate the present invention, but limit by no means Whole and definite broad ranges of the present invention are made, the scope should be by the appended claims table that proposes now or then Show.

Claims

1. heat transfer compositions, it is included：

(a) difluoromethane (R-32), in an amount of from 70 weights of trans-HFO-1234ze and R-32 gross weight in said composition Measure %-95 weight %；

(b) trans-HFO-1234ze, in an amount of from 5 weights of trans-HFO-1234ze and R-32 gross weight in said composition Measure %-30 weight %；

(c) third component, it is pentafluoroethane (R-125)；

Wherein described composition has the global warming up trend no more than 1000.

2. heat transfer compositions, it is included：

(a) difluoromethane (R-32), in an amount of from 45 weights of trans-HFO-1234ze and R-32 gross weight in said composition Measure %-55 weight %；

(b) trans-HFO-1234ze, in an amount of from 45 weights of trans-HFO-1234ze and R-32 gross weight in said composition Measure %-55 weight %；

(c) 1,1- Difluoroethanes (R-152a)；

Wherein described composition has the global warming up trend no more than 500.

3. the heat transfer compositions of claim 1, wherein HFC-32 and 5-30% weight of the composition by 70-95% weight Trans HFO-1234ze and HFC-125 composition, the content are each pressed relative to the trans HFO-1234ze in said composition Determined with HFC-32 gross weight.

4. the heat transfer compositions of claim 1, wherein HFC-32 and 5-25% weight of the composition by 75-95% weight Trans HFO-1234ze and HFC-125 composition, the content are each pressed relative to the trans HFO-1234ze in said composition Determined with HFC-32 gross weight.

5. heat transfer compositions, it is included：

(a) difluoromethane (R-32), in an amount of from the 50 weight %-70 weights of HFO-1234yf in said composition and R-32 gross weight Measure %；

(b) HFO-1234yf, in an amount of from the 30 weight %-50 weights of HFO-1234yf in said composition and R-32 gross weight Measure %；

(c) pentafluoroethane (HFC-125)；

6. the heat transfer compositions of claim 5, wherein HFC-32 and 30-50% weight of the composition by 50-70% weight HFO-1234yf and HFC-125 composition, the content each press relative to the HFO-1234yf and HFC- in said composition 32 gross weight measure.

7. any one of claim 1-6 heat transfer compositions, wherein the capacity of the composition is not less than R-22, R- substantially At least one of 404A, R-407C, R-410A or R-507, and the combination of their any two or more kind should in low temperature Capacity in.

8. any one of claim 1-6 heat transfer compositions, wherein the component (a), the component (b) and the component (c), when there is component (c), effectively to provide the presence of the amount of heat transfer compositions, the capacity of the composition is made to be not less than R- substantially 22nd, at least one of R-134a, R-404A, R-407C, R-410A or R-507, and their any two or more kind Combine the capacity in medium temperature application.

9. transfer heat to fluid or body or the method spread out of from fluid or body, this method are any in claim 1-6 including making The composition phase transformation of item simultaneously carries out heat exchange during the phase transformation with the fluid or body.

10. including the refrigerating system of the composition according to any one of claim 1-6, the system is selected from motor vehicle air conditioning system System, residential air conditioning system, market air-conditioning system, house refrigerator system, residential refrigerator systems, market refrigerator system, market refrigerator System, cooler air-conditioning system, cooler refrigerating system, heat pump, and the combination of they two or more.